Treatment of textile materials



Patented Mar. 31, 1936 TREATMENT OF TEXTILE MATERIALS Ernest William Kirk and :George Holland Ellis, Spondon, near Derby, England, assignors to Celanese Corporation of America, a corporation of Delaware No Drawing. Application September 30, 1932, "Serial No. 635,602. In Great Britain October '7 Claims.

This invention relates to processes for efiecting a reduction in the lustre of lustrous textile materials, particularly natural or artificial silk, by processes in which substantially white insoluble compounds are fixed on or in the materials, and

to other processes involving the fixation of insoluble compounds in textile materials, for example.

Weighting or mordanting.

As ordinarily spun, artificial silk, whether of the regenerated cellulose type or made of cellulose acetate or other cellulose esters or ethers, exhibits a high lustre and many methods have accordingly been devised for effecting a reduction in this lustre on account of the demand for products of subdued lustre. Reduction in lustre may for in-' stance be effected by incorporating finely divided white pigments or the like in the solutions from which artificial filaments are prepared. Again, the lustrous materials as ordinarily obtained may be delustred by, the fixation thereon or suitable white substances, such fixation being effected for instance by interaction of appropriate -reagents on the material. Thus, for instance,.cel

lulose acetate textile materials may bedelustred by interaction thereon of a titanium salt and a suitable reagent, in the manner described in U. S.

application Serial No. 635,043 filed September 27,

1932, corresponding to Britisliapplication" No. 2851'7/31 filed 14th .Oct0ber, 1931. As compared with methods involving .the incorporation of finely divided white substances in the spinning solutions,-this method possesses the advantage of being applicable to materials at any desired stage of their manufacture, for instance to'the materials 'while in yarn form or after they have been made into fabrics or evenafter the said fabrics have been dyed. We have now, discovered a further method of fixing titanium dioxide on artificial materials whereby the great advantages of the foregoing process may be secured in an enhanced degree, not only inre'spect of width of application but also asregards simplicity of oper ation and as regardsthe uniformity ,of the delustring, particularly when handling fabrics on large scale. I I a We have now found that delustring of textile materials by reaction of suitable reagents therein maybeefiected by a single bath'treatment if a careful selection of the reagents and/or the conditions under which they are applied is made. We have found for 'instancethat by addition of urea to a. solution of titanic sulphate or chloride,

a bath may be prepared which does not liberate titanium dioxide at all or only very slowly in the cold, though liberation of the titanium oxide comamino hydroxy compounds, e. g. amino-propanemences on heating, for, example to above 55-60 C. By immersion of cellulose acetate fabric for instance in such a bath and gradually raising the temperature of the latter, the material may be very satisfactorily and uniformly delustred in 5 a single operation, comparable as regards ease of execution with a simple dyeing process. As the delustring operation takes place slowly and progressively, the rate dependent upon the precise becomes an easy matter to produce any given degree of delustring, e. g. to delustre materials so as to match a given sample.

Broadly therefore in efiecting the formation of insoluble substances in textile materials, particu- 15 larly natural or artificial silk, by reaction of two or more reagents therein or thereon, the said reagents and/or their conditions of application are selected so that the desired insoluble substance I is only gradually formed therefrom. The inven- 20 tion is of particular, value in connection with the fixation of metallic oxides on natural or artificial silk, and more particularly for thefixation of substantially white metal oxides for the purpose of reducing the lustre of the materials. The in'- 25 vention will accordingly be more particularly described with reference to the fixation of metal oxides, the latter'being produced from thecorresponding metal salts by reaction with suitable of the metalo'xide in-question. Particularly use- '35.

ful results may be obtained by theemplo'yment of basic substances which, while capable of forming salts with acids, are scarcely or not at all ionized in aqueous solution i. e. substantially neutral bases. As examples may be mentioned urea 0 and its derivatives, e. g. methyl urea. and semicarbazide, amino carboxylic'or sulphonic acids,

e. g. glycine and other amino fatty acids, and

diol or other amino-, dior poly-hydroxy compounds. Such compounds as are water-soluble are of particular value. Urea in particular has been found especially, valuable as a reagent capable of effecting slow liberation of metal oxide composition of the bath and the temperature, it 10 reagents. 3 I,

bases with weak acids, for instance silicic or boric acids, or organic acids such as acetic acid. For example sodium acetate may be used with stannic chloride to produce a bath capable of slow liberation of stannic oxide. Again, in the case of aluminium salts, for instance, sodium silicate may be employed as a reagent adapted to form aluminium compounds therewith in the desired manner.

In carrying out the new process the delustring bath may be made up directly with the metal salt and the reagent adapted to react therewith in the required proportions, the material being simply immersed therein until the desired degree of delustre has been efiected. As indicated previously, the liberation of the metallic oxide may be facilitated by heating the bath, preferably gradually. If desired, however, instead of adding at first the whole of the reagent adapted to react with the metallic salt, the said reagent may be added intermittently or continuously during the delustring operation. Further, if desired, especially where as in the case of titanic salts the metal salt as normally occurring in commerce contains substantial quantities of free acid, a rela-.

tively strong alkali may be added to neutralize the acidity, but not to such extent as to cause any material precipitation. In the case for instance of preparing a delustring bath from titanium su1 phate or chloride, ammonia may be added to the latter in such quantity as to cause incipient precipitation. The acidity may for instance be adjusted to about pH 5. The urea or like body capable of causing gradual separation of titanium oxide is then added and the bath'is then ready for use. In preparing aqueous treatment'baths from metallic salts readily decomposed by warm or hot water, particularly titanic chloride, it has been found very advantageous to dilute the salt with an organic solvent such as alcohol therefor decomposition.

Any other desired additions may be made to the treatment baths used in accordance with the invention. For instance, in the case of treating materials consisting of or containing cellulose esters or ethers', the addition of a swelling agent or agents may be made, as for instance a thiocyanate, a water-soluble alcohol such as ethyl alco-1 hol,or a ketone such as acetone. Where suitable, organic swelling agents may be used for diluting titanium salts prior to addition of thenecessary water as described above. Alternatively or in addition the reagents themselves may be swelling agents for the materials under treatment, or be applied in such concentration or under such other conditions that they effect swelling. Again, if desired, protective colloids may be added in order to prevent the separation in the treatment baths of any metal oxide, when the latter. has

been liberated at a greater rate than that at which it can be taken up by the materials to be treated. It will be appreciated. that any such'protective colloids or other additions should be stable to the various constituents of the treatment baths. In the case of titanic or stannic salts for instance, the baths will usually be acid throughout the whole operation, and any protective colloid added should therefore be stable to acid. A suitable protective colloid in such case is a highly sulphonated oil or a. sulphuric ester of a higher aliphatic alcohol or a basic compound such as oleyl diethyl ethylene diamine. The bodies sold under the names sapamine CH and Sapamine MS have been found especially valuable.

As indicated previously, the reagents adapted to react withthe metal salts with formation of insoluble compounds are preferably water-soluble. The invention is not,.however, limited to this feature, as insoluble or d'iflicultly soluble reagents may be used. Such reagents may for instance be present in the treatment baths in finely subdivided form, subdivision being assisted if desired by the presence of dispersing agents. The range of reagents available for use in the process is thus greatly extended.

It has been found beneficial, especially when employing titanium compounds, to conduct the process in apparatus having the parts with which the liquid comes into contact made of non-metallic material, e. g. wood, or provided with enamel or other non-metallic coatings. In this way any tendency for metal compounds to be deposited on the walls or other parts of the apparatus may be minimized.

Though the metal salts and reagents adapted to react therewith are preferably mixed before application to the materials the invention is not restricted to this procedure. If desired for example, the urea or other reagent adapted to react with a metal salt, whether the reagent is applied in solution or in dispersion, may be applied to the materials prior to the application of the metallic reagent. Such application may be effected by padding for instance, the metallic reagent being applied in the same way or by a bath treatment or otherwise. In order to prevent or reduce loss of reagent from the materials during the treatment with the metallic or other second reagent, the latter may be applied or allowed to act under the conditions described in U. S. application Serial No. 628,367 filed August 11, 1932, corresponding to British application No. 25695/ 31 filed 14th September, 1931.,

The invention may be utilized in the treatment of textile materials of all kinds, and, as previously indicated, is of special value in efiecting the delustring of natural or artificial silk. Such artificial silk may be of any desired kind, for example of the regenerated cellulose type or of the kind consisting of cellulose acetate, formate, propionate or butyrate or other esters of cellulose, or of ethyl or benzyl cellulose or other cellulose others. If desired mixed materials may be treated, for instance materials consisting of natural silk or one of the aforementioned types of artificial silk in admixture with cotton, wool or other natural fibre. The materials may be coloured before or after the treatment in accordance with the new process.

The invention is illustrated but not limited by the following examples:-

Example 1 A cellulose acetate fabric is immersed in a 30:1 bath containing 2.25 per cent. of titanium sulphate based on the weight of the goods, 0.75 per cent. of ammonia (or just insufficient to cause any precipitation), l per cent. of urea and 0.5

- grams per litre of Gardinol R to serve as a wetting out agent and protective colloid. The fabric is worked at 30-35 C. for A hour in the bath which is then raised to 75 C., this temperature being maintained for a further hour. The fabric is then removed from the bath, washed and dried. A fabric of low lustre is thus obtained, the dulling being fast to repeated soapings and capable of 75 withstanding ordinary dyeing operations.

Example 2 into 5 litres of methylated spirit. This solution is then poured into a solution of litre of Sapamine MS solution in 40 litres of soft water. 5 kilos of anhydrous iron-free sodium acetate, previously dissolved in water, are then added with very good stirring, and finally a solution of 1 kilo of urea is added. This solution is then run into the machine, the total volume of the bath being about 2,200 litres, i. e. approximately :1. The fabric is worked for hour cold, andthe temperature then raised gradually to 75 C. The fabric is worked at this temperature for an hour, the bath dropped, and the fabric rinsed with two changes of water and dyed in the same machine.

Example 3 To delustre lbs. of cellulose acetate yarn. 550 grams of stannic chloride (anhydrous) are diluted to .5 litres with soft water. 50 cos. of Sapamine MS and 600 grams of sodium acetate (anhydrous) are also added. The whole is diluted to 300 litres and the yarn entered and turned for hour cold. The bath is then raised slowly to 70 C. and kept at this until the desired effect is" 2. Process for the delustering of textile materials which comprlses fixing a substantially white metal oxide thereon by slowly liberating the metal oxide in the presence of the materials in a bath prepared with a metal salt corresponding to the metal oxide and urea.

3. Process of delustering artificial silk of organic derivatives of cellulose which comprises forming titanium oxide therein by subjecting the artificial silk to the action of an aqueous bath prepared with a water-soluble titanic salt and urea.

4. Process of delustering cellulose acetate artificial silk which comprises forming titanium oxide therein by subjecting the artificial silk to the action of an aqueous bath prepared with a water soluble titanic salt and urea.

5. Process for the delustering of cellulose acetate artificial silk which comprises incorporating titanium oxide therein by subjecting the material to the action of a bath. prepared by diluting titanic chloride with an organic solvent, adding the dilution to an aqueous bath, neutralizing excess acidity by means of a relatively strong alkali in quantity insufficient to cause precipitation and then adding urea.

6. Process for the fixation of titanium oxide on textile materials which comprises subjecting the material to the action of an aqueous bath prepared with a water-soluble titanic salt and a neutral base.

7. Process for the delustering of cellulose acetate artificial silk which comprises incorporating titanium oxide therein by subjecting the material to the action of a bath prepared by diluting titanic chloride with an organic solvent, adding the dilution to an aqueous bath, neutralizing excess acidity by means of a relatively strong alkali in quantity insufllcient to cause precipitation and then adding a substantially neutral base. ERNEST WILLIAM KIRK. GEORGE HOLLAND ELLIS. 

